J . A m . Chem. SOC.1989, I l l , 751-753
75 1
UV Laser Photochemistry of Azoalkanes: Surprising Effects of Phenyl Substitution on the Lifetimes of 1,3-Cyclopentanediyl and 1,4-Cyclohexanediyl Triplet Diradicals Waldemar Adam,* Sven Grabowski,Ia and Herbert Platsch Institut f i r Organische Chemie der Uniuersitat Wiirzburg A m Hubland, 0 - 8 7 0 0 Wiirzburg, FRG
Klaus Hamemannib and Jakob W i n * Institut f u r Physikalische Chemie der Uniuersitat Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland
R. Marshall Wilson* Department of Chemistry, University of Cincinnati Cincinnati, Ohio 45221 Receiued August 17, 1988 Figure 1.
ORTEP view of 1 emphasizing the central coordination sphere.
Selected bond distances (A) and angles (deg) are as follows: Sn(1)Sn(2) = 3.4192 (4), -0(10) = 2.326 (2), -0(20) = 2.045 (2), - C I ( l l ) = 2.354 ( l ) , -C1(12) = 2.290 ( l ) , -C(122) = 2.113 (4), Sn(2)-O(10) = 2.035(2), -0(20) = 2.259 (2), -C1(21) = 2.363 ( l ) , -C1(22) = 2.297 ( l ) , -C(222) = 2.103 (5), Sn(1)-O(l0)-Sn(2) = 103.1 ( l ) , Sn(1)-0(20)-Sn(2) = 105.1 (1).
One might intuitively expect that the lifetimes of hydrocarbon diradical intermediates tend to increase upon phenyl substitution at the radical site. Indeed, 1,4-cyclohexanediyl (la), 3~ 50.1 ns,2 is over 3000-fold shorter lived than its phenyl derivative lb, 3~ = 275 m3 The effect of a second phenyl group, e.g. as in IC, ai R~ = R~~ H b)R1:Ph, R 2 = H c ] R1: R 2 z Ph
1 -
-2 -
on the triplet lifetime is difficult to anticipate because diradicals are not simply “double radical^".^ In fact, no systematic studies of the degree of phenyl substitution in simple hydrocarbon diradicals appear to have been reported at this time.5 However, an increase in lifetime has been observed with increasing chain length in phenyl-substituted polymethylene d i r a d i c a l ~ In . ~this ~ work we show that the effect of phenyl substitution on the lifetime of triplet 1,4-cyclohexanediyl differs dramatically from that of 1,3-cyclopentanediyl. The azoalkanes 36 and 4 were chosen as precursors for the diradicals 1 and 2 in this first systematic study on the effect of phenyl substituents on triplet lifetimes. The unknown azoalkanes Figure 2. ORTEPview of 4 emphasizing the central coordination sphere. Selected bond distances (A) and angles (deg) are as follows: Sn-O(1) = 2.091 (8), - N ( l ) = 2.32 ( l ) , -C(162) = 2.12 ( l ) , O(1)-Sn-0(1) = 157.0 (4), -N(1) = 71.2 (3), - N ( l ) = 89.0 (3), -C(162) = 86.5 (3), -C(102) = 105.3 (4), N(1)-Sn-N(l) = 63.3 (5), C(162)-Sn-C(162) = 118.7 (5), Sn-O(1)-C(11) = 122.8 (7).
Although an electrophilic mechanism for these aromatic C H bond activation processes seems reasonable, careful mechanistic studies are planned comparable to those both reported5 and underway on related d-block metal systems.15 Acknowledgment. We thank the National Science Foundation (Grant CHE-8612063) for support of the research. NSF support for the Crystallographic Unit at Purdue (Grant CHE-8615556) is also gratefully acknowledged. Supplementary Material Available: Expansions of the aromatic region of the ‘H N M R spectra of 1, 2, and 4 and tables of positional parameters, general temperature factors, and bond distances and angles (26 pages); tables of observed and calculated structure factors for 1 and 4 (37 pages). Ordering information is given on any current masthead page. (15) A very minor component from the reaction of SnCI4 with LiOAr2,6Ph2 was identified as the cage material [Li(p-OAr-2,6Ph2)$n]. Hence redox chemistry is a possible mechanistic complication: Smith, G. D.;Fanwick, P. E.; Rothwell, I. P. Inorg. Chem., in press.
k2 &{ F! 3 -
2: 2
a) ~ 1 R= ~ H= b ) d = P h , R 2 :H
R1
cl
$=R2= P h
4 -
4b,c were prepared by the usual triazolinedione route7 via the appropriate phenyl-substituted cyclopenta- 1,3-dienes.* The (1,) (a) Kekul6 Doctoral Fellow, 1985-87, Stiftung Volkswagenwerk. (b) Liebig Postdoctoral Fellow, 1986-88, Fonds der Chemischen Industrie. (2) Adam, W.; Hannemann, K.; Wilson, R. M. J . Am. Chem. SOC.1986, 108, 929. ( 3 ) Adam, W.; Grabowski, S.; Wilson, R. M.; Hannemann, K.; Wirz, J. J . A m . Chem. SOC.1987, 109, 7572. (4) (a) Salem, L.; Rowland, C. Angew. Chem., In?. Ed. Engl. 1972, 11, 92. (b) Caldwell, R. A. Pure Appl. Chem. 1984, 56, 1167. (c) Wirz, J. Pure Appl. Chem. 1984, 56, 1289. (5) (a) Scaiano, J. C. Acc. Chem. Res. 1982, 15, 252. (b) Wilson, R. M. In Organic Photochemistry; Padwa, A., Ed.; Dekker: New York, 1985; Vol. 7, Chapter 5. (c) Caldwell, R. A,; Majima, R.; Pac, C. J . A m . Chem. SOC. 1982, 104, 629. Mitzuno, K.; Ichinose, N.; Otsuji, Y.; Caldwell, R. A. J . Am. Chem. SOC.1985, 107, 5797. (d) Barton, D. H. R.; Charpiot, B.; Ingold, K. U.; Johnston, L. J.; Motherwell, W. B.; Scaiano, J. C.; Stanforth, S. J . A m . Chem. Soc. 1985, 107, 3607. (e) Zimmt, M . B.; Doubleday, D.,Jr.; Gould, I.; Turro, N. J. J . Am. Chem. SOC.1985, 107, 6724. Zimmt, M . B.; Doubleday, C., Jr.; Turro, N. J. Chem. Phys. Lett. 1987, 134, 549. (6) Engel, P. S.; Nalepa, C. J.; Horsey, D. W.; Keys, D. E.; Grow, R. T. J . A m . Chem. Soc. 1983, 105, 7102. (7) Adam, W.; De Lucchi. 0.Angew. Chem., In!. Ed. Engl. 1980, 19,762.
0002-7863/89/1511-0751$01.50/00 1989 American Chemical Society
752 J . A m . Chem. Soc., Vol. 111, No. 2, 1989
Communications to the Editor
Scheme I
Table I. Triplet Diradical Lifetimes ( 3 ~ )in Degassed Solution and Rate Constants for the Bimolecular Reaction with Molecular Oxygen 333nm iP$COI
(k10,lI"
Ph
~~
Ph 6 -
@& lOatm O2
Ph
Ph
+
Q Ph
triplet diradical
solvent
la lb
CFC1, benzene benzene MeCN n-C7H16
OOH
benzene benzene MeCN benzene
IC
Scheme I1
2a
n-C7H16
2bg
benzene MeCN benzene MeCN
2cg
c l R' =R2 = Ph
11 -
azoalkane 4c is thermally labile, having a halflife of only 30 min at 20 "C. Direct and triplet-sensitized (Ph,CO) laser photolyses (Coherent Supergraphite CR 18 and Innova 100 System argon ion laser) of azoalkanes 3c and 4b,c lead to the results shown in Schemes I and 11, respectively. Bicyclo[2.1. llhexane derivative 69 in the sensitized photolysis of 3c is a secondary photoproduct of diene 5, and the conversion of phenyl-substituted bicyclo[2.1.O]pentanes 9b,c to cyclopentenes 10b,c is caused by traces of acid. In the presence of molecular oxygen (10 atm), the benzophenone-sensitizedlaser photolysis of azoalkane 3c in CFC13 at -10 "C gave peroxides 7 (0.35%) and 8 (14%) and as remainder hydrocarbon 5; not even traces of the corresponding bicyclo[2.2.0]hexane could be detected. Under these conditions azoalkanes 4b,c led only to the endoperoxides llb,c. Peroxides 7 and 8 were isolated by means of flash chromatography on silica gel at -25 O C 9 An authentic sample of cyclic peroxide 7 was prepared by photooxygenationlo of 1,4-diphenyl-1,3-~yclohexadiene~~ and subsequent diimide reduction.I2 1,4-Diphenylbicyclo[2.1.O]pentane (9c) in benzene at 25 O C rapidly reacted with molecular oxygen to yield endoperoxide l l c . The lifetimes of triplet diradicals ICand 2b,c in degassed solution at ambient temperature were measured by flash photolysis using a XeF excimer laser (351 nm, 75-100 mJ, 25 ns).4c,13No transient absorptions were observed upon direct excitation of azoalkanes 3c,4b, or 4c. At azoalkane and benzophenone concentrations in the range of to M, most of the 351-nm radiation was absorbed by the benzophenone. The lifetime of triplet benzophenone, which was determined at 530 nm, was consistent with diffusion-controlled energy transfer to the azoalkanes. Biphasic decay curves, which fitted well to a dual exponential function, were observed in the 300- to 320-nm region: the faster decay rate was always equal to that of triplet benzophenone. The slower component was not affected by the addition of piperylene (up to 0.004 M) and was thus attributed to the triplet (8) (a) Riemschneider, R.; Nerin, R. Monatsh. Chem. 1960, 91, 829. (b) Wahren, R. J . Organomet. Chem. 1973,57,415. (c) Drake, N . L.; Adams, J. R., Jr. J . Am. Chem. SOC.1939, 61, 1326. (9) (a) All new compounds were fully characterized by elemental analyses and spectral data. (b) In the meantime the synthesis of the azoalkane 4c and the ESR spectrum of its triplet state diradical 2c have been reported, cf.: Corns, F. D.; Dougherty, D. A. Tetrahedron Lett. 1988, 29, 3753. For a preliminary account of our results cf.: Platsch, H.; Adam, W.; Hannemann, K.; Wirz, J. UV-Laser Photochemistry: Generation and Lifetimes of Phenyl-Substituted 1 ,3-Cyclopentadiyl Triplets; XI1 IUPAC Symposium on Photochemistry, Bologna, Italy, July 7-12, 1988; Abstr. PK-18, pp 328-329. (10) Kaneko, C.; Sugimoto, A,; Tanaka, S. Synthesis 1974, 876. (1 I ) Dale, J.; Kristiansen, P. 0. Acto Chem. Scand. 1971, 25, 359. (12) (a) Adam, W.; Eggelte, H. Angew. Chem., Int. Ed. Engl. 1977, 16, 713. (b) Coughlin, D. J.; Salomon, R. G. J . Am. Chem. SOC.1977, 99, 655. (13) Burnett, M. N.; Boothe, R.; Clark, E.; Gisin, M.; Hassaneen, H. M.; Pagni, R. M.; Persy, G.; Smith, R. J.; Wirz, J. J . Am. Chem. SOC.1988, 110, 2527.
'T
(ns)
k[O,] x 10-10 (M-I s-l)
